Method for coating target surfaces in the form of dielectric substances or ferroelectric crystals

ABSTRACT

The invention relates to supports consisting of nanoscalar polymer fibres, polymer tubes or hollow fibres for the application and targeted and/or delayed release of ingredients, in particular, agricultural active ingredients. The invention also relates to a method and a device for the production of supports of this type in a charged or empty state. The method and device use electrospinning technology.

The invention at hand concerns the use of nanoscaled, in particularnanostructured, polymer fibers as carriers or/and controlled releasesystems for agricultural active substances, a method for the delivery ofagricultural active substances, as well as a device for performing thisprocedure.

DESCRIPTION AND TECHNICAL STATE OF THE ART

Active substances known for the treatment of plants or/and soil, whichoccur naturally or are extracted by means of chemical methods or areproduced by means of chemical and/or microbiological processes, areunderstood to be “agricultural active substances”, such as, for example:fungicides, bactericides, insecticides, acaricides, nematicides,helminthicides, herbicides, molluscicides, rodenticides, algicides,aphicides, larvicides, ovicides, attractants in the form of animalnutriment, antifeedants, kairomones, repellents, game deterrents. Systemmeans are: plant growth regulators or plant nutrients, such as, e.g. butnot exclusively, fertilizer.

In particular, substances which impact the animals surrounding theplants are understood as insecticides As well as chemically ormicrobiologically produced substances, these substances can also benaturally-occurring active substandes, such as extracts, e.g. from theneem tree or the quassia root or also such substances which impact thesexual behavior of the animals surrounding the plants, such as e.g.pheromones.

It should be mentioned as an example for the commercial importance ofsuch substances that, in particular for the prevention of theinfestation of maize plants by the western corn rootworm (Diabroticavirgifera virgifera), several millions of euros are currently spentworldwide. In case of the infiltration of only this pest insect, whichhas not been detected until 2003, in Germany up to 25 millions of euroswould have to be spent for the protection of the maize plants, accordingto estimations of the Biological Federal Agency for Agriculture andForestry.

There is an entire array of methods known for the delivery ofsubstances, which can be applied to the soil or plants.

These are the delivery of

-   -   1) liquids in drop form through splashing, spraying, misting,        spreading as well as droplet irrigation,    -   2) solids in the form of granules and powders, as well as    -   3) gaseous substances through different types of dispensers.

Examples of 1 are the long-conventional methods for the delivery ordistribution, with watering can, hand sprayer, backpack sprayer,tractor, helicopter and airplane.

Examples of 2 are, along with granules and powders, also adsorbates onsolid natural or artificial particles, e.g. corncob pellets on which thekairomone MCA has been absorbed (Hummel and Metcalf, 1996; Hummel etal., 1997; Wennemann and Hummel, 2001). A lot of development work hasalready been spent on the technology of the dispensers. A criticaloverview of the state of the art achieved up to 1982 can be found in themonograph from Leonhardt and Beroza (1982). Further examples are foundin Hummel and Müller (1984). The method in 2 is typically used for thedelivery of fertilizer.

Examples of 3 are pheromones which are vaporized from half-open PTFEcapillaries, e.g. formulated with adhesive and distributed from airplane(Brooks et al., 1979). Also to be mentioned are double-chambereddispensers of the company Hercon Laboratories Corp., York, Pa., USA forpheromones, such as those which found use by the BASF AG company inpomiculture and viniculture. Finally to be mentioned are the“Lecture-bottle” buffer systems, described by Shorey et al. (1996), inwhich compressed signal substance solutions are stored and from whichformulations are dispensed through valves by radio command.

In the enclosed bibliography A, numerous sources are listed, in which acritical overview of the systems available until a short while ago ispossible.

The disadvantage of these methods is that, in general, the applicationof the active substances is not continuous, extends only over a verylimited space of time, and that disruptive factors such as wind and rainimpact this application as well as the time which the active substancesremain on the target surfaces (e.g. the soil in the area of plants to begrown or already grown or on the surfaces of plants) very negatively.This has the consequence that at a desired application of activesubstances over a long space of time a repeated delivery of the activesubstance is necessary, which is associated with raised costs. Thealternative of a nonrecurring delivery of the total amount of activesubstance bears the risk that the active substances are displaced tonon-targeted surfaces and, thus, at least a financial loss for the user,if not even undesired ecological effects presenting in non-targetedsurfaces. Evacuation through water into the soil or in lakes, brooks andrivers is a typical example.

Here, carrier materials or systems, as described for medicinal activesubstances but also active substances for agriculture, are advantageous.

The patent specification no. 703750 describes the production of tubes,tapes, pastes from polyvinyl chloride for therapeutic applications inbandages, medical clothing.

DE 19645919 A1 describes molds containing active substances on the basisof biologically degradable thermoplastic synthetics for combatingparasites, insects, which cause damage to plants, wherein the molds areavailable as tapes, medallions, earmarks or soil granules.

DE 19645842 A1 describes means for the treatment of plants, comprisingthermoplastically-processible, biologically degradable polymers providedwith at least one agrochemical active substance, whereby the applicationoccurs through molds, such as foils.

DE 10128531 A1 describes water-soluble or water-dispersable graftpolymerisates as coating material, packaging material or matrix creatorsfor agrochemicals.

DE 10115225 A1 describes molds containing active substances on the basisof thermoplastically-processible polyurethanes for combating parasites,wherein the molds are tapes and medallions. DE 19529409A1 describesthermoplastic and biologically degradable polymers, which, amongst otherthings, are suitable for delayed release of active substances.

DE 198 34025 A1 describes microcapsules for the controlled release ofactive substance.

DE 4206856 A1 describes fibers for protection against moths.

The patent specification 01266210 A describes bacterial and fungicidaltwines.

WO 99131963 describes polymer fibers for the growth of plants and as asoil substitute, as a cultivation medium, which contains means forgrowth.

D01F8114 describes microbacterial fibers and tissue for textiles.

EP 0799928 A1 describes fiber-shaped materials, which areantibacterially and antifungally equipped for applications in filters.

DE 101 16751 A1 describes likewise bioactive fiber products, which showantibacterial and fungicidal effects for the area of textiles. 08120524A describes hollow polymer fibers, which contain insecticides or flavoradditive in their core, wherein the release is controlled by the polymerwall.

077268772 A describes hollow fibers in the range between 7 and 150micrometers, which contain perfumes, antibacterial or fungicidal activesubstances in their interior. 05311509 A describes, finally, syntheticacryl threads with insecticidal qualities and good colorability.

DE 196 40 268 (BASF) describes foil-coated fertilizers, encompassingsingle coated volumes of a nutrient-containing substance, wherein thefoil coating the nutrient-containing substance contains awater-permeable polymer, which should preferably be biologicallydegradable. The method for the production of this fertilizer is verycomplex, since first the volumes are applied to a first foil, then asecond foil is applied, and then, through individual welding or similarmethods, both foils must be connected in the areas between the volumes.

Indeed, the subject matter of this DE 196 40 268 allegedly features theadvantage over the matters of the aforementioned specifications, e.g.DE-OS 40 35 223, WO 91/01086, or U.S. Pat. No. 4,845,888 that therelease of the active substances (fertilizer) occurs immediately afterthe delivery and in a targeted manner, contrarily to the releaseprofiles of the aforementioned applications, according to which therelease does not occur at the beginning, but after perforation orrotting of the carriers. However, the subject matter of DE 196 40 268 ischaracterized by, apart from limited choice options concerning thesuitable polymer materials (permeability for water vapor not higher than100 g/(m² and day)), the disadvantage that the “adjustability” of therelease, due to “transport blockades” (diffusion has been mentioned asthe main transport effect), is difficult. At the stated sizes of the“volumes”, i.e. the areas with fertilizers of 20 cm², the “transportpathways” from the area of higher fertilizer concentration to the wallcan easily result in being very high. Thus, from this, generallysmaller-structured carriers should be preferred.

None of these aforementioned substances or carriers, processes, inparticular for delivery, and methods, in particular for delayed release,is in the position to apply agricultural active substances, e.g.agrochemically functional substances, such as e.g. pheromones,insecticides, fungicides, extensively or/and very targeted and with avery low application of active substance per surface, or/and with verypronounced time-delay or/and with high spatial homogeneity inagriculture, forestry or in the garden loco-regionally targeted to thesoil or/and, in particular, plants, to maintain the active substances atthe site under different weather conditions, to adjust to the growth ofthe plant and, at the end of the growth period, to decompose intobiologically harmless substances or to decompose into substances whichnaturally occur in nature and in the concentrations encountered there.

Molds, such as those known in the technical state of the art, foils,tapes, medallions, hollow fibers, fibers in a diameter range clearlyover 1 micrometer are far from accomplishing these claims. In everycase, the ratio of surface to the volume of the carrier is fundamentalfor the adjustment of the release. This ratio is particularlyadvantageous in nanostructured fibers and increases very rapidly withdecreasing fiber diameter.

Already, several, in principle, suitable carriers of active substancesand their methods of production are known as results of “nano-research”.

Electrospinning represents a particularly economical method, both forthe gentle embedding of the active substances in the carrier, as well asfor control of the fiber diameter down to the nanometer scale.

Details to the process of electrospinning or electro spinning are, e.g.described in D. H. Reneker, I. Chun, Nanotechn. 7, 216 (1996) or Fong,H.; Reneker, D. H.; J. Polym. Sci, Part B 37 (1999), 3488 and in DE 10023 45 69.

In the case of electrospinning, the formation of fibers occurs by meansof a high electrical tension, attached between a nozzle and a counterelectrode (see Bibliography 1-10). The material to be spun is presenthereby in the form of a melt or/and a solution and is transportedthrough the nozzle. The electrical field causes a deformation of thedroplet leaving the nozzle via induced charges; a fine material flow isformed, which is accelerated in the direction of the counter electrode.The material flow is deformed hereby, reticulates—as in lighteningcharges—and is finally deposited onto a substrate. During the spinningprocess, the solvent evaporates or the melt cools, respectively.

The fibers are deposited at a rate of several meters per second; thefibers themselves can be produced up to a length of several meters. Theend result is a very fine fiber web on the substrate. Through adjustmentof the concentration of the solution, the attached fields, thetemperature, via the use of additives and further parameters, such asadditional electrodes, the viscosity, the processing temperature etc.,the achieved diameters of the fibers can be adjusted within a widerange. Fibers down to several nanometers can be achieved; hereby,extensive fiber arrangements up to the square meter scale can bedeposited on the substrate or the target surface.

Fibers from amorphous or partially-crystalline polymers, from blockco-polymers, from polymer alloys can be created in this way. Thus, e.g.,nanofibers were produced from natural and synthetic polymers as variousas polyamides, polycarbonate or polymethylmethacrylate, frompolynorbornene, from polyvinylidenfluoride, from cellulose, frompolylactides. The precise setting of the control parameters forelectrospinning is necessary for the respective material. Examples arethe material of the electrode, the form and arrangement of theelectrodes, the presence of auxiliary electrodes and controllingelectrodes, the viscosity of the melt or solution of the templatematerial, as well as their surface tension and conductivity. If theseparameters are not optimally chosen, then drops rather than fibers willbe deposited, the diameter lies in the micrometer scale or the diametersof the fibers fluctuate heavily. It is of importance for thecharacteristics of the fibers that, during electrospinning, it partiallyleads to an orientation of the chain molecules in the fibers, as wasshown via electron deflection on a fiber with a diameter of around 50nm. The orientations obtained are in fact of the same dimension as thefibers commercially heat-extruded.

A big advantage of electrospinning is that water can also be used as asolvent, so that water-soluble polymers, as well as water-solublebiological systems, can be spun. Examples are polyvinyl alcohol,polyvinylpyrrolidone, polyethylene oxide. Depending on arrangement andform of the electrodes, tissues are obtained, but also parallel strands.

Examples for results of the “nano-research” concerning this matter are:

i) DE 100 23 456 A1 (TransMIT, “Meso- and nanotubes”), wherein hollowfibers with an inner diameter of 10 nm to 50 μm and an outer wall, madeof metal-containing, inorganic compounds, polymers and/or metals, areproposed, which can be produced according to a first method, so that afiber from a first degradable material contains at least one coatingfrom at least one further material and, subsequently, the first materialis degraded, provided that the hollow fibers obtained in this wayfeature an inner diameter of 10 nm to 50 μm. As a second solution in theaforementioned specification, a method is proposed, whereby a fiber of afirst non-degradable material is coated successively with a second,degradable material and at least one further material, and the second,degradable material is degraded, provided that, based on the at leastone further material, a hollow fiber with an inner diameter of 10 nm to50 μm and a core from the first material is obtained. The subject matterof this specification, according to claim 21, was also foreseen forapplication in the area of “controlled release”.

ii) DE 100 40 897 A1 (TransMIT, “Production of polymer fibers withnanoscaled morphologies”), wherein porous fibers from polymericmaterials are proposed; the fibers feature diameters of 20 to 4,000 nmand pores (for instance, for the absorption of active substances) in theform of channels which at least reach the core of the fiber and/orthrough the fiber.

These fibers are to be produced according to claim 7 of the abovespecification, so that a 5 to 20 percent by weight solution of at leastone polymer in an easily vaporizable, organic solvent or mixture ofsolvents is spun by means of electrospinning at a field over 10̂5 V/m,wherein the resulting fiber features a diameter of 20 to 4,000 nm andpores in the form of channels which at least reach the core of the fiberand/or through the fiber. Hereby, surfaces of 100 to 700 m²/g can berealized. According to a preferable embodiment of the subject matter ofthis specification (column 4, paragraphs [0028] and [0029]), fibers,which initially do not feature channels, can also be produced by usingtwo polymers (one water-insoluble and one water-soluble). These,however, likewise show pores or channels, when, through exposure towater, the water-soluble polymers are dissolved within thepores/channels associated with them. For more precise productionconditions, refer to this specification.

If the surface is structured, then changes occur in, e.g. the wettingbehavior, the solution behavior and the degradation behavior, theadsorption behavior, and the ratio of surface to volume. The concept isto use a separation of phases initiated during electrospinning targetedfor the formation of such surface structures (8-10). Here, on one hand,the use of a binary system of one polymer and one solvent is possible.With very volatile solvents, electrospinning leads to a depletion of thesolvent and, with that, to a separation of phases under certainconditions, to the formation of a certain phase morphology, which thensubsequently causes a corresponding structuring of the fibers. Theregularity of the forming structure is noteworthy. Thus, this can beused very well for the production of unchanging, delaying carriers. Thepores possess an ellipsoidal cross section, wherein these, e.g. in thedirection of the fiber axis, are around 300 nm long and, perpendicularto that, 50 nm to 150 nm wide. The second way (see above DE 100 40 897A1) foresees the use of ternary systems polymer1/polymer2/solvent.During the formation of the fibers, a segregation of both polymersoccurs if they are incompatible. Fibers are produced with a binodal(dispersoid phase/matrix phase) or also co-continuous spinodalstructure. Such composite fibers are already interesting in themselves.If one of the two components is selectively removed, then fibers with aspecific surface structure result.

Unsolved up to now, however, was, in particular, the aim of how suchnanoscaled fibers (thickness up to 50 μm) could be produced as carriersin the desired “large surface scale” and homogeneity concerningagricultural crop land without being stocked with plants, or how thesecarriers could be applied in the desired “targetedness” to plants oreven to plant seeds, whereby the application of active substance pertarget surface (crop land surface, plant surfaces or seed surfaces)should be minimized.

AIM

Thus, the aim of the invention at hand was,

a) to provide for suitable carriers of agricultural active substances,which makes an improvement of the adjustability of the release possible

b) a method, with which the carriers, loaded or unloaded with activesubstance, can be released more cost-effectively in an extensive andvery targeted manner with high homogeneity as well as low use of activesubstance per target surface, and

c) to provide for a device, with which the carrier, loaded or unloadedwith active substance, can be released, according to the method based onthe present invention and its further advantages, directly.

Solution

Surprisingly, it was found that, with nanoscaled and/or nanostructuredpolymer fibers, considerably improved adjustability of the release ofagricultural active substances can be achieved.

Even as surprisingly, it was found that, with a modified electrospinningmethod using the farmland or one or/and several plants or/and plantseeds as counter electrodes,—in the case of pure farmland—a veryhomogenous, extensive delivery of carriers (loaded or unloaded withactive substances) can be realized with very high precision and a lowuse of active substance per target surface with simultaneouscommercially more advantageous conditions.

In trial experiments to be considered as a further sub-invention, therewas, likewise surprisingly, success in being able to “cocoon” othersimilar, aqueous biological systems, such as e.g. the extremities(hands, feet, arms, legs) or also other central body parts from humansor animals, in a relatively targeted manner. This is explained by thegood inducibility of an electric polarization of the water in thesebiological systems. Overall, it was also found that, generally,dielectric substances or ferroelectric crystals are excellently suitedas target surfaces for the electrospinning of polymeric solutions or/andmelt.

With this sub-invention it is also possible to design the method of thecoating of dielectric substances or the “cocooning” of plants to bedependant upon the moisture content of the target surfaces, i.e. withoutthe use of additional sensors.

For this reason, a corresponding device according to the presentinvention features the advantage that, e.g., in the relative movement ofthat device over farmland with series of plants in regular distances, aspinning method is only started at those plants, which, due tosufficient moisture content, form a sufficiently strong antipole to theelectric potential applied to the nozzle of the electrospinningapparatus.

In farmland without plants, the process of automatic spinning could alsobe carried out only on those farmland areas which feature a sufficientlyhigh moisture concentration.

The method according to a sub-part of the present invention is thus asgiven below:

method for the covering of target surfaces in the form of dielectricsubstances or ferroelectric crystals, preferably of bodies containingwater with nanoscaled fibers, wherein

the target surfaces are exposed to an electric potential and thus anelectric field and

emanating from a nozzle, which is situated on a higher electricpotential than the target surface, a solution or melt containing onepolymer is deposited onto the target surface.

At the core of this sub-invention and thus this method according to thepresent invention is the conclusion that the distribution of the charge,formed by polarization, on the target surface or surfaces in the form ofdielectric substances or ferroelectric crystals forms an antipoleeffective for the deposition of the polymer, together with the nozzle.

With respect to the aims mentioned further above, it must be stated,that the tasks a), b) and c) above are achieved by the subject mattersof the claims 1), 4) and 14).

In order to solve task a)

(the provision of carriers for agricultural active substances)

nanoscaled polymer fibers (up to a width of 50 μm) are suggested, whichwere created during the known process of electrospinning.

Particularly recommended are nanoscaled polymer fibers with a diameteri) from 10 nm to 50 μm, as known from DE 100 234 56 A1 (TransMIT, “Meso-and nanotubes”), and

ii) from 10 to 4,000 nm, as known from DE 100 40 897 A1 (TransMIT,“Production of polymer fibers with nanoscaled morphologies”).

Concerning the coating of the meso- and nanotubes from DE 100 234 56 A1refer to page 3 and 4 of this specification. With the methods namedthere or other methods for the functionalization of the tubes, asmentioned in the text, other such active substances as agrochemicals orthe active substances named here or also medicinally, can be fixed inthe hollow fibers. Finally, the outer wall of the fibers named there canalso be composed of a biologically degradable coating, i.e. degradableunder such conditions that can be found in agriculture. Examples ofwater-soluble materials are polyvinyl alcohol, polyvinylpyrrolidone,polyethylene oxide.

Those polymer fibers with nanoscaled morphologies, according to DE 10040 897 A1, can, as represented on page 4, also be produced withwater-soluble polymer components (see page 4 for examples). These aremixable beforehand with the agricultural active substances representedhere. Finally, in this way, nanoscaled morphologies can be produced,from which the desired agricultural or also medicinal active substancesare released in a delayed manner.

The mentioned nanoscaled fibers can be applied onto fields by the knownmethods (see above 1) to 3)), i.e. by spraying, misting, sprinkling,etc.

In the technical state of the art, the electrospinning technology isknown (DE 100 23 456 “Meso- and nanotubes” refers, concerning the basicsof this technology, to EP 0 005 035, EP 0 095 940 and US 5 024 789 or WO91/01695, for example.). The general advantage of the electrospinningmethod is that with this method—in comparison with the state of the art,such as other spinning, methods, for example the extrusion spinningprocess—noticeably narrower fibres are producible and the fibresextracted in this way feature a noticeably higher surface to volumeratio.

In order to solve task b)

(the provision of a process for the delivery of such carriers)

it was decisive that, surprisingly, the known process of electrospinningis also feasible outside of laboratory conditions and mobile as well,with the necessary delivery speed, and a properly target-oriented“cocooning” of single plants or seeds (in the opened furrow and beforecovering with soil, or also before transfer to a field) is possible.Even with relative movement of plants/seeds or farmland in relation tothe electrospinning apparatus, more than 10,000 sqm of a “nanoweb” canbe delivered per day.

In this, the farmland or/and plants or/and seeds are used as a counterelectrode. If necessary, additional counter electrodes are to beforeseen in the surrounding area of the plants or seeds, in order toimprove the targeting of the spinning process.

The method foresees for integration of the active substances in thepolymer nanofibers through blending or mixing of the polymer (or thepolymer mixture) and its solvent (or solvent mixture) or its melt (ormelt mixture) with the desired agricultural active substances before theprocess of the actual spinning.

The release of the active substances can be controlled, e.g., viadiffusion and dimensions of the fibers, degradation of the fibers,dissolution of the fibers or permeation out of the fibers.

A further advantage of the method is that the process of integration ofthe active substances in the carriers and the delivery of thecarriers/of the active substance system in nature can occur on-site (noseparate packaging and storage of the carriers and active substances,etc.) and in one step.

The addition of a further biologically degradable coating, for examplefor the purpose of even more precise control of the diffusion or thepermeation of the active substances or for the protection of the fibers,e.g. from UV rays (in delivery/spreading of the fibers to plants), canoccur, for example, by the method of chemical vapor deposition, whichthen occurs after the exit of the fiber from the spinning nozzle orthrough other deposition methods not affecting the electric field.

Furthermore, a further coating can occur through a furtherelectrospinning process, wherein the fiber emanating from the firstnozzle features such a potential that polymers with the desired coatingmaterials emanating from a second nozzle are deposited on the firstfiber.

A further method known as co-electrospinning (see “Compound Core-ShellPolymer Nanofibers by Co-Electrospinning”, Zaicheng Sun, Eyal Zussman,Alexander L Yarin, Joachim H. Wendorff, Andreas Greiner; Adv. Mat.15(22), pp. 1929-1932 (2003)) foresees a core- and a coating-fiber,which are basically produced simultaneously through electrospinning. Forthat purpose, as illustrated/depicted in the aforementioned publicationunder FIG. 1, the same electric potential is applied to two syringe-likecontainers arranged coaxially to one another and in one another, whichfeature separated chambers for the intake of two identical or differentpolymers (or polymer mixtures, in solution or/and in melted form).However, a metallic plate in the form of a copper plate was used as acounter electrode with another electric potential. With the methoddescribed there, even otherwise non-electrically spinnable polymers orsubstances (or mixtures thereof), such as poly(dodecylthiophenes) (PDT)in chloroform solution or even metal salt solutions such as Pd(OAc)₂ intetrahydrofuran solution, were able to be electrically spun as an innercore-fiber with electrically spinnable polymers as a coating-fiber (inthe first case with poly(ethylene oxide) in chloroform solution and inthe second case with poly(l-lactide) in chloroform solution).

This method is thus particularly suitable as a method for the coating ofpolymers, which are not or very poorly electrically spinnable, as well.

Particularly suitable as a protective additive against UV radiation is,e.g. a coating made of ZnO_(x)S_((1-x)), preferably in crystalline form,particularly preferable in crystalline form according to the Wurtzittype, wherein this coating can also be realized on-site (thus in-situ,see above). For production, the substrate, in this case the nanoscaledfibers, is coated with the novel coat with one of the known thin-filmdeposition methods, e.g. with the sputter technique, the chemical vapordeposition from gas phases (CVD, MOCVD), through vaporization, throughpyrolysis. Surprisingly, it was found that the mixed system ZnOS can becompletely mixably synthesized as a crystalline thin-film and, in theproduction, the parts of 0 and S can be adjusted in the entire area(from x=0 to x=1), wherein the optical functional film resulting thereoffeatures a sharp absorption edge with very high transmission at higherwave lengths and very low transmission at lower wave lengths—incomparison to the absorption edge.

For delaying the release of active substances, here of agriculturalactive substances as well, the permeation of the active substances (ifnecessary, in solution with other polymers) through polymer films isexceptionally suitable.

Suitable polymer films for delaying the release through permeation(and/or diffusion) comprise or contain:

-   polymers, such as poly-(p-xylylenes), polyvinylidenhalogenides,    polyester, polyether, polyolefines, polycarbonates, polyurethanes,    natural polymers, polycarboxylic acids, polysulfonic acids, sulfated    polysaccharides, polylactides, polyglycosides, polyamides, polyvinyl    alcohols, poly-α-methylstyrenes, polymethacrylates,    polyacrylnitriles, poly-(p-xylylenes), polyacrylamides, polyimides,    polyphenylenes, polysilanes, polysiloxanes, polybenzimidazoles,    polybenzothiazoles, polyoxazoles, polysulphinides, polyesteramides,    polyarylene-vinylenes, polyetherketones, polyurethanes,    polysulfones, ormoceres, polyacrylates, silicones, fully aromatic    co-polyesters, poly-N-vinylpyrrolidones,    polyhydroxyethylmethacrylates, polymethylmethacrylates, polyethylene    terephthalates, polymethacrylonitriles, polyvinyl acetates,    neoprene, buna N, polybutadienes, polytetrafluorethylene, modified    or unmodified celluloses, α-olefines, vinylsulfonic acids, maleic    acids, alginates or collagens.

The monomers, which form the basis of the polymers, can carry one orseveral functional groups respectively, whereby it can concern a singleor different types of substituents. It concerns the following functionalgroups:

-   H, linear or branched alkyl, alkenyl, alkinyl, cycloalkyl,    cycloalkenyl, cycloalkinyl, phenyl, phenylalkyl, phenylalkenyl,    phenylalkinyl, phenylcycloalkyl, phenylcycloalkenyl,    phenylcycloalkinyl, cycloalkyl-alkyl, cycloalkyl-alkenyl,    cycloalkyl-alkinyl, heterocyclic compounds, heterocyclo-alkyl,    heterocyclo-alkenyl, heterocyclo-alkinyl, linear or branched alkyl    sulfonate, alkenyl sulfonate, alkinyl sulfonate, linear or branched    alkyl benzene sulfonate, alkenyl benzene sulfonate, alkinyl benzene    sulfonate, aminosulfonyl-alkyl, aminosulfonyl-alkenyl,    aminosulfonyl-alkinyl, aminosulfonyl-cycloalkyl,    aminosulfonyl-cycloalkenyl, aminosulfonyl-cycloalkinyl, linear or    branched alkylsulfonamide, alkenyl-sulfonamide, alkinyl-sulfonamide,    cycloalkyl-sulfonamide, cycloalkenyl-sulfonamide,    cycloalkinyl-sulfonamide, phenyl-sulfonamide, heterocyclo-sulfonic    acid, heterocyclo-sulfonamide, heterocyclo-alkyl-sulfonic acid,    heterocyclo-alkyl-sulfonamide, heterocyclo-alkenyl-sulfonic acid,    amide- or ester-like bound linear and/or branched chain aliphatic    sulfonic, carboxylic and/or phosphonic acid, styrene-sulfonic acid,    anetol-sulfonic acid, styrene phosphonic acid, heterocyclo-alkenyl    sulfonamide, heterocyclo-alkinyl-sulfonic acid,    heterocyclo-alkinyl-sulfonamide, aryl-sulfonic acid,    aryl-sulfonamide, aryl-alkyl-sulfonic acid, aryl-alkyl-sulfonamide,    aryl-alkenyl-sulfonic acid, aryl-alkenyl-sulfonamide,    aryl-alkinyl-sulfonic acid, aryl-alkinyl-sulfonamide, alkyl-,    alkenyl, alkinyl-, aryl-, heteroalkyl-, heteroaryl-carboxylic acids,    esters thereof, carboxylic acid amides thereof, amino acids,    orthologous phosphonic acid derivatives of all sulfonic acids    listed, hydroxy-alkyl-, hydroxy-alkenyl-, hydroxy-alkinyl-,    hydroxy-cycloalkyl-, hydroxy-alkyl-cycloalkyl-,    hydroxy-cycloalkyl-alkyl-, hydroxy-phenyl-, hydroxy-alkyl-phenyl-,    hydroxy-phenyl-alkyl-groups, as well as the orthologous amino- and    thio-compounds, polyethoxy-alkyl, polyethoxy-alkenyl,    polyethoxy-alkinyl, polyethoxy-cycloalkyl, polyethoxy-cycloalkenyl,    polyethoxy-cycloalkinyl, polyethoxy-aryl, polyethoxy-alkyl-aryl,    polyethoxy-heterocycloalkyl, polyethoxy-heterocycloaryl, alkenal,    alkanal, alkinal, cycloalkenal, benzyl carbaldehyde,    heteroaryl-carbaldehyde, benzyl-alkyl-carbaldehyde,    heteroaryl-carbaldehyde, aliphatic heteroalkyl-alkenal,    hetero-alkenyl-alkenal, hetero-alkinyl-alkenal, alkanon, alkenon,    alkinon, cycloalkyl-alkanon, dicycloalkanon, arylalkanon,    heteroaryl-alkanon, imines, halogens and halogenated derivatives of    all groups listed, nitriles, isonitriles, sulfonic acid esters,    phosphonic acid esters, nitro compounds, hydroxylamines, allyl    compounds, adenosine-3′,5′-monophosphate,    adenosine-3′,5′-diphosphate, adenosine-3′,5′-triphosphate,    guanosine-3′, 5′-monophosphate, guanosine-3′, 5′-diphosphate,    guanosine-3′,5′-triphosphate, dextran sulfate cellulose, cation    exchanging groups, anion exchanging groups. Preferably, therein,    -   alkyl refers to a group with 1 to 20 carbon atoms    -   alkenyl and alkinyl refer to a mono- or polyunsaturated group        with 3 to 20 carbon atoms    -   the heterocyclic groups refer to an R group with 1 to 20 carbon        atoms, wherein up to 5 carbon atoms can be replaced by        heteroatoms, which are selected from the group nitrogen, oxygen,        sulfur, phosphorus    -   aryl refers to an aromatic R group with 5 to 20 carbon atoms    -   heteroaryl refers to a corresponding aromatic R group, in which        up to 5 carbon atoms can be replaced by heteroatoms from the        group nitrogen, oxygen, sulfur, phosphorus.

Such films have, as e.g. in the example of polylactides shown furtherbelow, already been produced through electrospinning, in particular inthe form of hollow fibers, i.e. the wall of the hollow fiber formed thepolymer film functioning as the permeation barrier. Such films are,however, also able to be deposited as an electrospun coating layer on anelectrospun core-fiber.

In order to solve task c) (device) an electrospinning device isrecommended, which features a voltage supply source able to deliver anelectrical current of between 1 and 100 kV, as well as anozzle/tip/syringe electrically connected therewith. Preferably, thedevice features storage means, or/and for mixing of the used polymers,solvents and agricultural active substances. The device for theproduction and delivery of the loaded or unloaded carriers is preferablyattached to a tractor in a mobile manner and preferably uses the sameenergy source as the tractor as an energy source for the generation ofelectrical current. Alternatively, the device also features means ofconverting and, if necessary, storing energy in form of electricalenergy.

In an advantageous practical embodiment, the device according to thepresent invention features at least one counter electrode electricallyand/or mechanically connected to the device, for improved control of thedelivery process, which features a different electrical potential to thenozzle or tip used as the first electrode for the passage of thepolymer(s).

If, e.g., two counter electrodes, each to the left and right of a plantrow, are arranged beneath the device moved over the field, then, ifnecessary, with use of further control electrodes, delivery of thecarrier targeted only on these plants can be carried out.

A further, quite particularly advantageous practical embodiment for themethod and device results, when for further increased specific or moretargeted delivery, i.e., for example depending on the local groundcomposition or the condition of any one plant or down to each individualleaf, one or several optical sensors according to DE 44 13 739 are usedin order to use the infrared radiation emanating from the ground or aplant or a leaf for identifying a plant (compared to normal farmland) orto identify the local composition of a soil or plant and to return thecorresponding control commands to the device. (See claim 1 for themethod and claim 2 and following claims of the specification quotedabove for the relevant set-up).

In a further advantageous practical embodiment it is foreseen that asecond, then outer nozzle/tip/syringe is provided coaxially to a first,then inner nozzle/tip/syringe. Both of the two nozzles/tips/syringes canbe connected for the supply of polymers to the melt or solution to itsown or a shared storage container. In addition, storage containers forthe active substances can also be foreseen.

Preferably, the device also features pressurizing means, whichpressurizes one or both of the containers provided, in order to supplythe nozzle(s)/tip(s)/syringe(s) with polymers and/or active substances.Hereby, the blending or mixing of the polymers with the activesubstances can take place in the storage container or on the flow routeto the nozzle, for instance by means of a collective flow route ofpolymer and active substance up to the tip of the device, which isarranged in such a way that turbulences in the flow and, thus, ablending of polymers and active substances can be observed.

Both of the nozzles or tips of the device feature the same electricalpotential. For the production of multilayered fibers the device canfeature further nozzles or tips, which are arranged around therespectively interior nozzle.

Examples for Agricultural Active Substances are:

Examples for Fungicides are:

-   2-aminobutane; 2-anilino-4′-methyl-6-cyclopropyl-pyrimidine;    2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoromethyl-1,3-thiazol-5-carboxanilide;    2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide;    (E)-2-methoxyimino-N-methyl-2-(2-phenoxyphenyl)-acetamide;    8-hydroxychinoline sulfate; methyl-(E)-2-    2-[6-(2-cyanophenoxy)-pyrimidine-4-yloxy]-phenyl-3-methoxyacrylate;    methyl-(E)-methoxyimino[alpha-(o-tolyloxy)-o-tolyl]acetate;    2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine,    azaconazole, benalaxyl, benodanil, benomyl, binapacryl, biphenyl,    bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate,    calcium polysulfide, captafol, captan, carbendazim, carboxin,    chinomethionat (quinomethionate), chloroneb, chloropicrin,    chlorothalonil, chlozolinate, cufraneb, cymoxanil, cyproconazole,    cyprofuram, dichlorophen, diclobutrazol, dichlofluanid, diclomezine,    dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph,    diniconazole, dinocap, diphenylamine, dipyrithione, ditalimfos,    dithianon, dodine, drazoxolon, edifenphos, epoxiconazole, ethirimol,    etridiazole, fenarimol, fenbuconazole, fenfuram, fenitropan,    fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin    hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, fluoroimide,    fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol,    folpet, fosetyl-aluminum, phthalide, fuberidazole, furalaxyl,    furmecyclox, guazatine, hexachlorobenzene, hexaconazole, hymexazol,    imazalil, imibenconazole, iminoctadine, iprobenfos (IBP), iprodione,    isoprothiolane, kasugamycin, copper preparations, such as: copper    hydroxide, copper naphthenate, copper oxychloride, copper sulfate,    copper oxide, oxine-copper and Bordeaux mixture, mancopper,    mancozeb, maneb, mepanipyrim, mepronil, metalaxyl, metconazole,    methasulfocarb, methfuroxam, metiram, metsulfovax, myclobutanil,    nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol,    ofurace, oxadixyl, oxamocarb, oxycarboxin, pefurazoate, penconazole,    pencycuron, phosdiphen, pimaricin, piperalin, polyoxin, probenazole,    prochloraz, procymidone, propamocarb, propiconazole, propineb,    pyrazophos, pyrifenox, pyrimethanil, pyroquilon, quintozene (PCNB),    sulphur and sulphur preparations, tebuconazole, tecloftalam,    tecnazene, tetraconazole, thiabendazole, thicyofen,    thiophanate-methyl, thiram, tolclophos-methyl, tolyifluanid,    triadimefon, triadimenol, triazoxide, trichlamide, tricyclazole,    tridemorph, triflumizole, triforine, triticonazole, validamycin A,    vinclozolin, zineb, ziram,    8-tert.-butyl-2-(N-ethyl-N-n-propyl-amino)-methyl-1,4-dioxa-spiro-[4,5]    decane,    N-(R)-(1-(4-chlorphenyl)-ethyl)-2,2-dichlor-1-ethyl-3t-methyl-1r-cyclopropanecarboxylic    acid amide (diastereomer mixture or isolated or single isomers),    [2-methyl-1-[[[1(4-methylphenyl)-ethyl]-amino]-carbonyl]-propyl]-carbamic    acid 1-methylethyl ester and 1-methyl-cyclohexyl-1-carboxylic    acid-(2,3-dichlor-4-hydroxy)-anilide.

Examples of Bactericides are:

-   bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,    kasugamycin, octhilinone, furancarboxylic acid, oxytetracycline,    probenazole, streptomycin, tecloftalam, copper sulphate and other    copper preparations.

Examples of Acaricides, Insecticides and Nematicides are:

-   abamectin, acephate, acrinathrin, alanycarb, aldicarb, alphamethrin,    amitraz, avermectin, AZ 60541, azadirachtin, azinphos A, azinphos M,    azocyclotin, Bacillus thuringiensis,    4-bromo-2-(4-chlorphenyl)-1-(ethoxymethyl)-5-(trifluoromethyl)-1    H-pyrrole-3-carbonitrile, bendiocarb, benfuracarb, bensultap,    betacyfluthrin, bifenthrin, BPMC, brofenprox, bromophos A,    bufencarb, buprofezin, butocarboxim, butylpyridaben, cadusafos,    carbaryl, carbofuran, carbophenothion, carbosulfan, cartap,    chlorethocarb, chlorethoxyfos, chlorfenvinphos, chlorfluazuron,    chlormephos,    N-[(6-chloro-3-pyridinyl)-methyl]-N′-cyano-N-methyl-ethanimidamide,    chlorpyrifos, chlorpyrifos M, cis-resmethrin, clocythrin,    clofentezine, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin,    cyhexatin, cypermethrin, cyromazine, deltamethrin, demeton-M,    demeton- S, demeton-S-methyl, diafenthiuron, diazinon,    dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion,    diflubenzuron, dimethoate, dimethylvinphos, dioxathion, disulfoton,    edifenphos, emamectin, esfenvalerate, ethiofencarb, ethion,    ethofenprox, ethoprophos, etrimfos, fenamiphos, fenazaquin,    fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb,    fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fenthion,    fenvalerate, fipronil, fluazinam, fluazuron, flucycloxuron,    flucythrinate, flufenoxuron, flufenprox, fluvalinate, fonofos,    formothion, fosthiazate, fubfenprox, furathiocarb, HCH, heptenophos,    hexaflumuron, hexythiazox, imidacloprid, iprobenfos, isazophos,    isofenphos, isoprocarb, isoxathione, ivermectin, lambda-cyhalothrin,    lufenuron, malathion, mecarbam, mevinphos, mesulfenphos,    metaldehyde, methacrifos, methamidophos, methidathion, methiocarb,    methomyl, metolcarb, milbemectin, monocrotophos, moxidectin, naled,    NC 184, nitenpyram, omethoate, oxamyl, oxydemeton M, oxydeprofos,    parathion A, parathion M, permethrin, phenthoate, phorate,    phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M,    pirimiphos A, profenophos, promecarb, propaphos, propoxur,    prothiofos, prothoate, pymetrozine, pyraclofos, pyridaphenthione,    pyresmethrin, pyrethrum, pyridaben, pyrimidifen, pyriproxifen,    quinalphos, salithion, sebufos, silafluofen, sulfotep, sulprofos,    tebufenozide, tebufenpyrad, tebupirimiphos, teflubenzuron,    tefluthrin, temephos, terbam, terbufos, tetrachlorvinphos,    thiafenox, thiodicarb, thiofanox, thiomethon, thionazin,    thuringiensin, tralomethrin, triarathene, triazophos, triazuron,    trichlorfon, triflumuron, trimethacarb, vamidothion, XMC, xylylcarb,    zetamethrin, substituted propargylamines, as shown in DE 102 17 697,    dihalogenpropene compounds, as shown in DE 101 55 385, pyrazolyl    benzyl ether, as shown in DE 199 61 330, pyrazole derivatives, as    shown in DE 696 27 281.

Examples of Herbicides are:

-   anilides, such as e.g. diflufenican and propanil; aryl carboxylic    acids, such as e.g. dichlorpicolinic acid, dicamba and picloram;    aryloxyalkanoic acids, such as e.g.

2,4-D, 2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP and triclopyr;aryloxy-phenoxyalkanoic acid esters, such as e.g. diclofop-methyl,fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl andquizalofop-ethyl; azinones, such as e.g. chloridazon and norflurazon;carbamates, such as e.g. chlorpropham, desmedipham, phenmedipham andpropham; chloroacetanilides, such as e.g. alachlor, acetochlor,butachlor, metazachlor, metolachlor, pretilachlor and propachlor;dinitroanilines, such as e.g. oryzalin, pendimethalin and trifluralin;diphenyl ethers, such as e.g. acifluorfen, bifenox, fluoroglycofen,fomesafen, halosafen, lactofen and oxyfluorfen; ureas, such as e.g.chlortoluron, diuron, fluometuron, isoproturon, linuron andmethabenzthiazuron; hydroxylamines, such as e.g. alloxydim, clethodim,cycloxydim, sethoxydim and tralkoxydim; imidazolinones, such as e.g.imazethapyr, imazamethabenz, imazapyr and imazaquin; nitriles, such ase.g. bromoxynil, dichlobenil and ioxynil; oxyacetamides, such as e.g.mefenacet; sulfonylureas, such as e.g. amidosulfuron,bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron,metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl,thifensulfuron-methyl, triasulfuron and tribenuron-methyl;thiocarbamates, such as e.g. butylates, cycloates, diallates, EPTC,esprocarb, molinates, prosulfocarb, thiobencarb and triallates;triazines, such as e.g. atrazine, cyanazine, simazine, simetryne,terbutryne and terbutylazine; triazinones, such as e.g. hexazinone,metamitron and metribuzin; others, such as e.g. aminotriazole,benfuresate, bentazone, cinmethylin, clomazone, clopyralid, difenzoquat,dithiopyr, ethofumesate, fluorochloridone, glufosinate, glyphosate,isoxaben, pyridates, quinchlorac, quinmerac, sulphosate and tridiphane.

Chlorocholine chloride and ethephone shall be named as examples forplant growth regulators.

Common inorganic or organic fertilizers for the provision of plants withmacro-and/or micronutrients are named as examples for plant nutrients.All common substances applicable in preparations of this type areconsidered as addithies which can be contained in the agriculturalactive substances according to the present invention. Preferably, fillermaterials, greases and lubricants, softening and stabilizing agentsknown in synthetic technology are preferably to be considered.

Examples of Filler Materials are:

-   table salt, carbonates, such as calcium carbonate or sodium hydrogen    carbonate, further aluminium oxides, silicic acids, aluminas,    precipitated or colloidal silicium dioxide, as well as phosphates.

As examples of greases and lubricants shall be mentioned:

-   magnesium stearate, steraric acid, talcum and bentonite.

All substances, which are used in their common form for this purpose inpolyesteramides, are considered as softening agents.

Esters of phosphoric acids, such as dimethylphthalate anddioctylphthalate, and esters of adipinic acids, such as diisobutyladipate, further esters of azelaic acid, malic acid, citric acid, maleicacid, ricinoleic acid, myristic acid, palmitic acid, oleic acid, sebacicacid, stearic acid, and trimellitic acid, as well as complex linear polyesters, polymer softening agents and epoxidized soybean oils.

Antioxidants and substances which protect the polymers from undesireddegradation during processing are considered as stabilizing agents. Allcommonly applicable dyes for agricultural active substances can becontained as dyes in the active substances according to the presentinvention. The concentrations of the individual components can be variedwithin a larger scale in the agricultural active substances.

Production Examples for Nanoscaled Polymer Fibers

Examples for the production of nanoscaled polymer fibers are known fromDE 100 40 897 A1 (TransMIT, “Production of polymer fibers withnanoscaled morphologies”) or DE 100 234 56 A1 (TransMIT, “Meso- andnanotubes”).

Method Examples

One first polymer is mixed or blended with active substance or/and asecond polymer of the same type and then with an active substance, in aspinning apparatus, i.e. located in the nozzle or the storage containerattached to the nozzle. A first electrical potential is applied to thenozzle and if necessary to the storage container, which features adifferent value to the target surface(s) arranged in a spaced manner tothe nozzle, whereupon a thin, fiber- shaped mold made of a mixture ofthe aforementioned substances is deposited on the target surface orsurfaces. The at least one polymer can hereby exist in the form of asolution or a melt. In the latter case, a heating of the nozzle or/andthe storage container can be foreseen. The mixture/blend of polymer andactive substance can also take place within the device, at the latest,however, on the flow route to the nozzle of the device.

For the delivery of the active substances, the corresponding device ismoved relatively to the farmland or the plants on the ground, whereinthe method of application with seeds can be carried out as a partialstep of a sowing as well, such as for example in DE 43 39 443 (Amazonenfactories), preferably before covering the seeds with soil. In thiscase, the furrows made by the plow or/and the seeds serve as a counterelectrode.

It has been shown that a plant can be nearly completely “cocooned” withthis process.

For improving the degree of extensive “spinning”, the method can becarried out while moving the nozzle or tip/syringe of theelectrospinning device relatively to the direction of movement of thedevice or of target area, preferably above the plant. Alternatively,several nozzles can be foreseen next to one another in a circular formor on the left and right of one or several plant rows, which can also beoperated alternatingly, so that extensive “cocooning” occurs. It hasbeen shown in experiments that 10 and more nozzles can be used parallelto one another, whereby, then, 10 plant rows or furrows can be “spun”parallelly.

A further example for the execution of the method, i.e. the “cocooning”of plants, is shown in the following for the plants maidenhair fern andbaby's tears. For proof of the durability of the fibers as carriers inthe form of nanoscaled polymers, poly(lactide) was chosen here.

No active substance was integrated, as the integration is already knownin the technical state of the art. Thus, numerous, soluble activesubstances, in particular in the solution of the polymers used, as wellas medicinal active substances, such as dexamethasone etc., were alreadyintegrated by the work group of the inventor's work groups.

In these experiments, a counter electrode (second electrode), which isnot entirely necessary, was foreseen beneath the plants (situated in aclay pot, respectively). The first electrode consisted of a centrallyperforated disc, to which, compared to the second electrode (counterelectrode), a low electric potential (20.15 to 30.25 kV) was applied.The nozzle featured a metallic tip with a diameter of 0.3 mm (interior),which penetrated the central opening of the perforated disc, and waslocated in electric contact with the perforated disc (i.e. at the sameelectric potential), wherein the tip protruded downwards below the levelof the perforated disc.

Due to the low viscosity of the polymer solution chosen here, a storagecontainer in a cylindrical form with a volume of 2 ml was fixed mountedabove the tip, so that the device altogether featured the form of asyringe.

At a feed of the piston of 1 cm/hr, at a flow of the polymer solution of0.7 ml/hr, a state of equilibrium between removal of the materialthrough electrospinning and feeding by moving the piston was thus ableto be achieved.

Poly(lactide) fibers with a diameter of 1 to 2 μm were deposited on amaidenhair fern and a baby's tears from a solution by electrospinning.The conditions during spinning were

maidenhair fern baby's tears concentration of the solution 4 wt % 4 wt %solvent (boiling pt.) Dichloromethane Dichloromethane distance betweenthe electrodes 38.0 cm 21.7 cm height of the plant max. 38 cm  9.2 cmdiameter of the plant max. 40 cm   12 cm distance between syringe andvaried 12.5 cm plants tension (syringe) 20.0 kV 15.0 kV energy (syringe) 175 nA n.d. tension (counter electrode) 30.0 kV 25.0 kV energy (counterelectrode)  205 nA n.d.

In particular in long-branched plants, such as the maidenhair fern, ithas been shown that a relative movement of the plant to the nozzle(first electrode) is advantageous, in order to shorten the duration ofthe “spinning”.

Regarding the durability of the fibers, it was determined that thefibers adhered securely to the plants even after months. The growth ofthe plants—in particular of the baby's tears—was not influenced by thefiber mat deposited in a planar manner.

Examples of Device

The device according to the present invention features the meansincluded in the description of the method, whereby for operation justone energy source and one electrically connected nozzle, tip/syringe areessential for the passage of the polymer. Preferably, at least onestorage container for the polymer and active substance connected to thenozzle, if necessary with means of mixing or/and means of heating, (inthe case of melts, instead of solutions) is foreseen.

For the improved control of the passage of the mixture of polymer andactive substance a pressure device is foreseen, which exerts pressure onthe mixture in the direction of the nozzle outlet. This pressure devicecan be connected to the optimal control of the flow speed of the mixturewith a control device, which itself is connected to a transducer, suchas flow or streaming speed sensors.

In the case of melts or also with rapidly changing operatingtemperatures (delivery in winter/spring or summer) it is advantageous toconnect the supplied heating device for pre-warming the melt or themixture or solution with the signaller and one or more temperaturesensors.

In this way, the continual delivery of nanoscaled polymer fibers whichremain the same (with or without active substances) can be controlleddepending on the actual values of the flow or streaming speed in theno77Ie or nozzle tip or depending on the temperature or temperatures ofthe melt/the mixture/the solution.

Preferably the device is designed to be mobile so that it can be movedover plants or farmland. A stationary device can also be foreseen, inorder to be used, for instance, in greenhouses, where for example plantboxes or similar can be moved relatively to the device.

Plant seeds can also be webbed with a stationary device of theaforementioned type, which move for example on a conveyor beltrelatively to the device. In both of the above cases (greenhouse,cocooning of plant seeds) it is advantageous when the plants or theplant seeds to be cocooned are exposed in a targeted manner through acounter electrode (second electrode), for instance in form of a metalframe, to an electrical field around the plants, for instance in theplant boxes of a greenhouse, or around or above a conveyor belt with theplant seeds spread on it. For the homogenous webbing of the plants orplant seeds it can be advantageous to apply alternating voltage.

Preferably, for application on the field, the energy source receives viaadapted transformers, its energy from the drive device of the devicecarrying tractor. For the simultaneous processing of several plant rowsor field sections the device features several nozzles or hoses for theoutput of the carriers, which for example can be arranged in pairs oneto the left and one to the right of the plant row.

In a further practical embodiment the nozzles are attached to moveablearms, which are arranged in a stretched position for operation and areable to be moved for road transport into a second position, whereby thearms in the latter position are arranged parallel and next to eachother. Preferably the arm parts and distances between the nozzlesfeature the size and distance ratios given in DE 100 41 148 A1 (claim1).

For increasing the “plaiting” of the carriers (nanoscaled fibres) to beobserved, in particular with plants, in a particularly preferableembodiment the device features further means of moving the nozzlesrelatively to the plants. These means can be active means such aselectric motors or similar or passive means, such as flow blade elementswhich use the air stream caused by the movement of the whole device formoving the nozzles. Likewise, the connection of electrical alternatingvoltage is suitable in order to cause an increased plaiting of thenanoscaled fibers with the plants.

In a further practical embodiment, the device can feature means for themeasurement and steering or/and control of the amount of carriersdelivered (mass, volume or surface of the nanoscaled fibers or tubes),e.g. in the form of a scale or in the form of optical recognition meanse.g. in connection with a flow meter (which can also be designed in theform of an inductive flow meter for the reduction of the flowresistance). Alternatively, a flow rate meter, in connection with theknown nozzle diameter, can also give information about the amount ofcarriers delivered per time unit in the form of nanoscaled fibers ortubes. In particular, these means could be used for the calibration ofthe device, which should be carried out corresponding to the seasonalchanges of the environmental influences, in order to adjust the correctparameters, respectively, for the desired delivery per time unit orsurface before the start of delivery. Naturally, the speed of therelative movement of the device to plants or soil or plant seeds shouldalso be considered in this. The calibration before the start of deliverythus assumes that the relative movement is carried out with the desiredspeed for a predefined period of time and, correspondingly, the targetrequirements for the mass to be delivered, the parameter pressure on themixture, the solution or the melt, temperature(s) on/in the nozzle orthe mixture, the solution or the melt, are varied in such a way, untilthe desired actual value agrees with the target requirements.

A further advantageous practical embodiment for the device (and also forthe method) foresees that a device for the creation of a high voltagealternating current between the first electrode (nozzle of the device)and the counter electrode (or electrodes, i.e. the target surface orsurfaces). Thus, the degree of “plaiting” with the target surfaces bythe fibers can be increased.

This alternating current can also be created mechanically and,preferably, by one or several movable, preferably rotating nozzles inthe form of hooks or bar-shaped electrodes.

In a particularly preferable practical embodiment, the device featurestwo or more nozzles arranged coaxially to one another for the output ofthe polymer(s). Preferably, the output openings of all of these nozzlesare located in a plane and feature the same electric potential, so thatco-electrospinning is able to be carried out by means of these nozzles,so that a core- and a coating-fiber can be produced.

In a further embodiment, the device features other means for coating ofthe nanoscaled fibers emanating from the first nozzle (i.e. the firstelectrode). These means are preferably the known means for the executionof thin-film deposition methods, e.g. the means of sputter technology,the chemical vapor deposition from gas phases (CVD, MOCVD), vaporizationtechniques and pyrolysis.

It is immediately clear to persons skilled in the art that, inparticular, the carriers known from DE 100 234 56 A1 (TransMIT, “Meso-and nanotubes”) and DE 100 897 A1 (TransMIT, “Production of polymerfibers with nanoscaled morphologies”) also feature as such a use foragriculture.

The latter exists in the natural substance “air”, which allows fortilling of the same when introduced into the soil. The bonding of waterin these carriers results in an agricultural “use”.

It is likewise clear to persons skilled in the art that other biologicalsystems with a similarly high percentage of water can also be covered orcoated with a “nano”-web with the method introduced here. In addition,e.g. the extremities of humans or animals also count, wherein,naturally, the agricultural substance would have to be replaced bymedicinal or veterinarian substances. The conditions for the “webbing”of these other biological systems (extremities or entire bodies) arecomparable in all parameters, such as typical potential differences,currents, distances etc., as long as it is comparable to the moisturecontent of the target surfaces.

BIBLIOGRAPHY

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1-21. (canceled)
 22. Method for the coating of target surfaces in theform of dielectric substances or ferroelectric crystals, preferably ofbodies containing water with nanoscaled fibers, wherein the targetsurfaces are exposed to an electric potential and, thus, an electricfield and, emanating from a nozzle, which is set at a higher electricpotential than the target surface, a solution or melt containing apolymer is delivered to the target surface.